DE2426266A1 - CARBON PREPARATIONS FOR INCORPORATION IN MINERAL BINDERS - Google Patents

Description

GERMAN GOLD AND SILVER SCHEIDEANSTALT FORMERLY ROESSLER 6000 - Frankfurt am Main, Weißfrauenstrasse 9

Carbon black preparations for incorporation into mineral binders.

The invention relates to aqueous carbon black preparations containing wetting agents for incorporation into mineral binder systems, e.g. for concrete, roofing stone, exposed concrete, asbestos concrete and exterior plaster formulations.

These carbon black preparations are used for outdoor weathering and permanent black pigmentation of mineral binder systems, in which they are incorporated.

It is known to use aqueous mineral binder systems, e.g. a cement-sand mixture, for coloring pigment dispersions add and then connect the setting process. For the production of black-colored systems it is also known to use carbon black dispersions, which contain wetting or dispersing agents should be ignored.

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It is known that carbon black is produced in a number of different grades. It. gives flame, furnace and gas resp. Channel black. The existing differences in particle size, surface structure, surface size, pH values and density , have different wetting behavior and dispersibility of the types of soot. According to these different properties, ranging from hydrophilic to hydrophobic, different wetting or dispersing agents are used. In the case of, for example, very non-polar carbon blacks, wetting agents are used during manufacture of aqueous carbon black dispersions added in order to make the carbophilic surface of the starting carbon black somewhat more hydrophilic. In addition, surface-active substances such as wetting or dispersing agents are used Added in the production of carbon black dispersions in order to optimally distribute the carbon black used and to stabilize the degree of distribution.

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As wetting agents or dispersants, anion-active or non-ionogenic substances such as alkylarylsulfonates, lignosulfonates or polyethylene glycol derivatives are used.

The carbon black dispersions produced therewith are usually liquid, paste or powder systems. Their composition can e.g. consist of approx. 35 parts water, 60 parts Carbon black (pigment) and 5 parts of wetting agent.

When these known carbon black dispersions are used, it has been found that the weathering stability of correspondingly colored binder systems, for example for roof tiles, leaves something to be desired in that the depth of color decreases sharply on prolonged weathering of the surface. What this weathering phenomenon can be traced back to has not yet been proven. There were therefore doubts as to whether the previously customary carbon black dispersions could be used instead of inorganic pigments, such as Fe ₃ O ₄ or red iron oxide, while maintaining a comparable quality standard. O··

I) surprisingly, it has now been found that when using certain carbon black preparations, preferably produced in powder form, have a significantly increased weathering stability of Carbon black pigmented mineral binder systems can be obtained.

The invention relates to aqueous carbon black preparations containing wetting agents for incorporation into mineral binder systems e.g. for concrete, roofing stone, exposed concrete, asbestos concrete and Exterior plaster formulations, which are characterized by a content of fluorine-containing wetting agents to increase the Weather stability.

Roof tiles made using the same recipes and processes and are only found in the circulating or dispersing agents used were differentiated for over a year

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Exposed to weathering and then compared with corresponding return samples. The roof tiles, with which wetting or dispersing agents according to the prior art, showed a significant variation in color depth from the Return samples. They were heavily bleached.

In contrast, the roof tiles showed which shredding or dispersing agents were used according to the invention, no lightening compared to the return samples. They were identical to the unweathered sample stones.

As fluorine-containing wetting or dispersing agents are anion-active and. suitable for non-ionic agents.

Alkali salt of arylsulfonic acid perfluoroalkene ether belong to the first group and show a good effect. They are, for example, by reacting a perfluoroalkene of the general formula C _n ]? 2 _n > where η is eg = 10, preferably C ₁₀ F ₂₀ with a polyethylene glycol of the general formula HO- (CH ₂ -CH ₂ -O) _n -H, where η zvB. = 23 , preferably made with HO- (CH ₂ -CH ₂ -O) ₂₅ -H ■.

That at. Perfluoroalkene of the general formula CL used as the starting substance for both types of wetting agent, e.g. with the size η = 10, is a branched hydrocarbon. This preferably has the structure (C ₂ F ₅ ) ₂ (CF ₃ ) CC (CF ₃ ) = CF (CF ₅ ) with the gross formula C ₁₀ F ₂₀ .

_{If the perfluoroalkene C 10} F _{20 is} used in the preparation of the alkali salts of the aryl sulfonic acid perfluoroethers, the anionic wetting agent of the formula C ₁₀ F ₁₉ -OC ₆ H ₄ -SO ₃ Na is obtained.

A preferred, nonionic _{wetting agent produced with the perfluoroalkene C 10} F ₂₀ from the group of polyethylene glycol bisperfluoroalkene ethers has the structure C ₁₀ F ₁₉ -0- (CH ₂ -CH ₂ -O) _{s -3} -C ₁₀ F ₁₉ .

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The wetting agents can be used in amounts of $ 0.02-0.4, preferably from $ 0.08 to $ 0.3 based on the weight of the carbon black will. The amount of wetting agent used depends on the individual case according to the composition of the binder system, in particular according to the type of carbon black used, and also go beyond this Letting agent quantities come into question.

For the pigmentation of concrete roof tiles, carbon blacks of the class LFI (Long Flow Impingement), RCC (Regular Color Channel), MCF (Medium Color Furnace), FCFm (Fine Color Furnac.e 'modifide), FCF (Fine Color Furnace) have proven themselves as proved particularly useful. Mixtures of these carbon blacks can also be used. The use of fluorine-containing wetting agents or dispersants provided in the context of the invention ensures optimum distribution of the carbon black and the stabilization of the distribution _r : .- * .- degree in an aqueous carbon black preparation, with a broad range in relation to the type of carbon black used. There is a possibility of variation.

The influence of those used according to the invention is extremely favorable fluorine-containing wetting or dispersing agent on the coloristic appearance, i.e. the weathering retarder of the mineral Binders into which the carbon black preparations according to the invention are incorporated are. Even after one year of weathering, as can be seen from the examples, preserve with the invention Soot preparations, pigmented mineral binders give their coloring character. - ■ "

The invention is explained below with the aid of a few exemplary embodiments explained in comparison to the state of the art:

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I. Production of the carbon black preparations

Example 1- (on the state of the art)
92 g special black 4

1 g Vanisperse CB = Oxylignine (lignin sulfonate) 5 g of water

2 g silica VN 3 = precipitated silica 100 g

The soot is placed in the Retschmühle, size 0, and the required quantities of whetting agent and water for about 5 minutes admitted. Thereafter, it is rolled over for 30 minutes.

Example 2

80 g special black 4
0 ^ gC ₁₀ F ₁₉ -OC ₆ H ₄ -SO ₃ Na

19.8 g water
100 g
This approach is processed as described in Example 1.

Example 3

80 g special black 4
0.2 g C ₁ ^ F ₁₉ -O- (CH ₂ -CH ₂ -O) ₂₃ -C ₁₀ C ₁₉

19.8 g water
100 g
This approach is processed as described in Example 1.

The carbon black special black 4, used in Examples 1 to 3, has the following characteristics:

Electron microscopic particle diameter: 25 m / u Tamped density DIN 53194: 0.19 g / l

Oil requirement FP: 300 $ (g / 100g)

pH value: 3

Surface: 180 m ² / g.

It belongs to the LFI (Long Flow Impingement) class.

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Example 4 (on the prior art)

.'92 g flame black 101. 1 g Tanisperse CB = oxylignin (lignin sulfonate) 2 g silica VN 3 "= precipitated silica

5 ff water 100 g '
This approach is processed as described in Example 1.

Example 5

80 .- g flame black 101 0.2 g C ₁₀ F ₁₉ -OC ₆ H ₄ -SO ₃ Na

19.8 g water 100 g
The batch is processed as described in Example 1.

Example 6 . ... _y

80 g flame black 101 0.2 g C ₁₀ F ₁₉ -O- (CH ₂ -CH ₂ -O) ₂₃ -C ₁₀ F ₁₉

19.8 g water 100 g
The batch is processed as described in Example 1.

The carbon black lamp black used in Examples 4 to 6 has the following characteristics:

Electron microscopic particle diameter: 95 m / u Tamped density DIN 53194: 0.31 g / l Oil requirement FP: 280 $ (g / 100 g) pH value: 7
Surface: 21 m ² / g.

It belongs to the MCF (Medium Color Furnace) class

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Example 7

92 g Printex A

1 g Vanisperse CB = Oxylignine (lignin sulfonate)

2 g silica VN 3 = precipitated silica 5 g water

The batch is processed as described in Example 1.

Example 8

80 g Print ex A 0.2 g C ₁₀ P ₁₀ -OC ₆ H ₄ -SO ₃ Na

19.8 g of water

100 g ·.

"The batch is processed as described in Example 1.

Example ^ ''" ^? 80 g Printex A

0.2 g C ₁₀ P ₁₀ -O- (CH ₂ -CH ₂ O) ₂₃ -C ₁₀ F ₁₉ , 19.8 -. ^ G water 100 g
The batch is processed as described in Example 1.

The Printex A carbon black used in Examples 7 to 9 has the following characteristics:

Electron microscopic particle diameter: 41 m / rev Tamped density DIN 53194: 0.30 g / l

Oil requirement: -3OO <fo (g / ioOg) ■

pH value: 8

Surface 46 m ² / g. ■

It belongs to the MCP (Medium Color Furnace) class.

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Example 10 (on the prior art)

92 g of L-TD carbon black

1 g Vanisperse CB = Oxylignine (lignin sulfonate)

2 g silica VN -3 1 = precipitated silica 5 U water

The batch is processed as described in Example 1.

Example 11

80 g carbon black L-TD 0.2 g C ₁₀ P ₁₉ -OC ₆ H ₄ -SO ₃ Na

19.8 g water 100 g
The batch is processed as described in Example 1.

Example 12 ... {.-

80 g carbon black L-TD 0.2 g C ₁₀ F ₁₉ -O- (CH ₂ -CH ₂ -O) ₂₃ -C ₁₀ F ₁₉

19.8 g water 100 g
The batch is processed as described in Example 1.

The L-TD carbon black used in Examples 10 to 12 has the following characteristics:

Electron microscopic particle diameter: 35 m / rev Tamped density DIN 53194: 0.17 g / l Oil consumption FP: 360% (g / 100 g) pH value: .8 Surface: 80 m ² / g It belongs to class RCC (Regular Color Channel) .

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II. Production of the sample stones Example 15

Corresponding to the incorporation of the carbon black preparations according to the invention the examples 1 to 12 in mineral binders • the following procedure is used:

5 g of the carbon black preparation according to the invention according to the examples 1 to 12

100 g cement (EPZ 275)
300 g sand (0 - 3.15 mm)
25 g of water

This batch was mixed in a mortar mixer for 10 minutes.

For the production of sample stones, the mixture obtained according to the example is filled into a mold and pressed into sample ^{stones by means of an oil pressure press at 300 kgf / cm 2.}

These sample stones are dried at room temperature (24 ° C).

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In order to test the weathering behavior, the stones according to Example 13 were exposed to weathering for one year. The location was on the roof of an industrial building and faced south. The sample stones were compared with non-weathered return samples every 4 months. It was found here that the samples of Examples 1, 4, 7-10 were already a tad lighter than the reverse samples after 4 months.

The pattern after 12 months showed a significant deviation from the return patterns for all the pattern stones of Examples 1, 4, 7, 10 that had been weathered. An exception were those stones which contained carbon black preparations obtained in accordance with Examples 2, 3, 5, 6, 8, 9, 11 and 12. Here the weathered stones (in terms of color depth) were identical to the patterns. _T

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Optical measurements confirmed the above subjectively obtained results. The spectrophotometric method according to DIN 5033 (device ^: Elrep "ho / Zeiss) was used. ■ -.'- ■ - · ·

The table below gives the values for some with different Wetting agents restored stones. The values Y, which result from the difference between the weathered and the ■ yielded to unweathered stone.

Wetting agent used Γ weathered minus Yunweathered

Lignin sulfonate (oxylignin)

(Examples 1, 4, 7, 10) 7.4

Wetting agent (corresponding to the · ■ · >

Examples 2, 5, 8, 11) 1.9

Wetting agent, cent. the

Examples 3, 6, 9, 12) 1.8

Example 14

A soot preparation in a 200 kg batch according to the following recipe on the pan mill is used to color the concrete manufactured:

80 parts of carbon black Printex A

0.1 part of wetting agent C ₁₀ F ₁₉ -0- (CH ₂ -CH ₂ -O) ₂ 5-C ₁₀ P ₁₉ 19.9 parts of water
100 parts

The Printex A carbon black has the characteristics given for Examples 9 to 12.

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The soot is placed in the pan and the wetting agent previously dissolved in the required amount of water for 15 minutes admitted. After the addition of the water-hardening agent had ended, it was rolled for 60 minutes.

The entire approach is made after rolling with a Progress hammer mill ground with sieves and then filled into water-repellent, polyethylene-coated bags. '.

The carbon black preparations, which can be easily produced on this scale, had the desired properties. They let in well mineral binder systems according to the invention, such as concrete systems, which then incorporate the inventive exhibited good weather-stable behavior.

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Claims (12)

- 12 claims Aqueous carbon black preparations containing wetting agents for Incorporation into mineral binder systems, e.g. for concrete, roofing stone, exposed concrete, asbestos concrete and Exterior plaster formulations, characterized by a content of fluorine-containing wetting agents to increase the Weather stability. 2. Carbon black preparations according to claim 1, characterized in that an anion-active wetting agent is used. 3. Carbon black preparations according to claim 1, characterized in that ■ that a nonionic wetting agent is used. 4. carbon black preparations according to claim 2, characterized in that that alkali salts of an Ar; y \ l ^ lfonsäureperfluoralkäthers as wetting agents be used. 5. 'Soot preparations according to claim 3, characterized in that that polyethylene glycol bisperfluoroalkene ethers are used as wetting agents. 6. Carbon black preparations according to claims 1-5, characterized by a wetting agent content, based on the weight of the carbon black, of 0.02-0.4 $, preferably from 0.08 to 0.3 ? *. 7. Carbon black preparations according to Claims 1-6, characterized in that that soot of the class LPI (Long Plow Impingement) is used. ' 8. Carbon black preparations according to Claims 1-6, characterized in that that RCC (Regular Color Channel) class carbon black is used. 509850/0534 9. Carbon black preparations according to claims 1 ^ 6, characterized in that that carbon black of the class FCFm (Fine Color Furnace Modifide) is used. 10. Carbon black preparations according to claims 1-6, characterized in that that carbon black of the MCF (Medium Color Furnace) class is used. 11. Carbon black preparations according to claims 1-6, characterized by that carbon blacks of the class FCF (Fine Color Furnace) ' be used. 12. Carbon black preparations according to claims 7-11, characterized in that that carbon blacks are used in mixture. PL / Dr.W-IS
Development No. 31/74
May 2, 1974 50985 0/0534